US 3923517 A
A method for rapidly forming photographic images which comprises processing a photographic light sensitive material comprising at least one silver halide emulsion layer, and a gelatin derivative-containing upper most layer at a temperature of at least 30 DEG C.
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Description (OCR text may contain errors)
United States Patent 1191 Yamamoto et al.
1 1 Dec. 2, 1975 l5 METHOD FOR RAPIDLY FORMING PHOTOGRAPHIC IMAGES |75| inventors: Nobuo Yamamoto; lkutaro Horie;
Kiyotaka Hori; Shigeru Nagatomo; Hidei'umi Sera; Kenji Yokoo, all of Kanagawa, Japan Fuji Photo Film Co., Ltd.. Minami-ashigara. Japan 22 Filed: Feb. 14, 1974 211 Appl, No: 442,556
I 73 I Assignee:
[301 Foreign Application Priority Data Feb. 15, 1973 Japan 1. 4848624  US. Cl 96/50 R; 96/63; 96/66 R;
96/67; 96/87 R; 96/95; 96/114 [511 Int. CH... GO3C 5/26; 003C 5/24; (103C 1/72 Primary ExaminerMary F. Kelley Attorney, Agent. or Firm-Sughrue, Rothwell, Mioi Zinn & Macpeak  ABSTRACT A method for rapidly forming photographic images which comprises processing a photographic light sensitive material comprising at least one silver halide emulsion layer, and a gelatin derivative-containing upper most layer at a temperature of at least 30C.
[9 Claims, No Drawings METHOD FOR RAPIDLY FORMING PHOTOGRAPHIC IMAGES BACKGROUND OF THE INVENTION photographic images with good quality using photoin graphic processings at elevated temperatures.
2. DESCRIPTION OF THE PRIOR ART In general, photographic light-sensitive materials contain a hydrophilic natural high molecular weight substance and/or a hydrophilic synthetic high molecular weight substance, as well as gelatin, in a silver halide emulsion layer. a photographic auxiliary layer such as an intermediate layer, a protective layer or an antihalation layer, or in a subbing layer interposed between these layers and a support. Photographic materials containing these hydrophilic high molecular substances are usually processed, after exposure, in various aqueous solutions which differ from each other in pH, salt concentration and solution temperature in the steps of development, stopping, fixing and washing (and bleaching in the case of color light-sensitive materials), in order to form photographic images.
However, where the processing temperature is high as in the case of rapid processing (i.e. the procedure of rapidly conducting development or other photographic prnccssings to form images) of photographic light-sensit c materials or where the processing requires much time because of a number of steps for various purposes are involved as in the case of processing reversal color photographic materials, the photographic emulsion layers and other layers of the photographic light-sensitive materials become swollen and softened to too great a degree. This results in many disadvantages such as a reduction in the physical strength, the frequent formation of a network pattern called reticulation", and an increase in the drying load after processing.
Removal of these disadvantages is preferable because they seriously reduce the commercial value of photographic light-sensitive materials regardless of whether the photographic materials are black-and-white lightsensitive materials or color light-sensitive materials.
In recent years, with the development of methods of processing photographic light-sensitive materials, it has been desired to conduct the photographic processing not at temperatures near room temperature of about 20C or 24C, but rather at elevated temperatures such as at 30C, 3 8C or 50C, whereby each processing step can be shortened and the productivity in the photographic processing steps can be increased. Therefore, it is necessary to develop an image-forming technique using photographic light-se nsitive materials which have excellent physical properties so that the abovedescribed defects are not encountered even with rapid processing at an elevated temperature.
In the prior art relating to the satisfying of the abovedescribed requirements, the previous incorporation in a photographic layer or a protective layer of a hardener (upon production of the photographic light-sensitive materials) in a very large amount e.g., on the order of several times or several 10 times as much as in the ordinary case, was considered so as to impart sufficient physical strength to resist severe processing conditions. However, although reticulation could be prevented to some extent, this method failed to prevent reticulation to a completely practical extent. In addition, in this method, the phenomenon in which the physical strength of the emulsion film undergoes a gradual change during storage of the photographic light-sensitive material, known as post-hardening", tended to take place, which made the maintainance of photographic quality difficult. Furthermore, this method had the disadvantage that the degree of hardening of the photographic layers was increrased to such an extent that permeation and diffusion of a developer upon development processing was afiected, which lead to a substantial reduction in sensitivity.
Other methods such as a method of processing an exposed photographic light-sensitive material in an aqueous solution bath. called a pre-hardening bath". containing a hardener immediately before developing the material, a method of conducting development and hardening at the same time using a developer containing a hardener, and like methods are known.
However, these methods have the disadvantages that fog, deterioration of other photographic properties and, particularly with color light-sensitive materials, color stain, and similar unfavorable phenomena occur, such that the kind of appropriate light-sensitive materials and processing conditions as well as the kind of the hardener are narrowly limited, in order to obtain photographic layers possessing the necessary physical strength within a short period of time without deteriorating photographic properties. In practicular, because an additional pre-hardening bath step is contained in the former method, this method cannot be said to be an excellent method since the shortening of the photographic processing time and the simplification of the processing steps are not obtained.
Additional method for controlling reticulation include a method of coating carboxymethylated casein or ethyl cellulose sulfate sodium salt in advance on the uppermost layer of the emulsion side as a replacement for a gelatin protective layer usually employed in a photographic light-sensitive material. This method is believed to be advantageous in that the addition of a large amount of hardener to photographic layer is not required. However, carboxymethylated casein has the disadvantage that removal therefom of impurities which adversely affect the photographic properties is difficult. An additional production disadvantage is that it is difficult to form a uniform coating layer of this material on an emulsion layer due to the poor coating propety of an aqueous solution of carboxymethylated casein. Also, it is difficult to prepare an ethyl cellulose sulfate sodium salt having good solubility in water with good reproducibility. As can be surmized from the chemical structure of this sulfuric acid ester, the ester has a poor storage stability over a long period of time, lacks a setting property, and has poor coating property. Thus, these materials are not necessarily suitable in the production of photographic light-sensitive materials.
It is, therefore, an object of the present invention to provide a method for rapidly forming images with good quality by processing a silver halide photographic lightsensitive material at an elevated temperature.
Another object of the present invention is to provide an excellent photographic light-sensitive material in which softening or reticulation of the photographic layer does not take place during or after rapid processing at an elevated temperature.
A further object of the present invention is to provide a method for producing a photographic light-sensitive material having practical productivity, photographic properties and physical properties, and for conducting photographic processing thereof at a high temperature without deteriorating these characteristics, thus rapidly obtaining images with high quality.
SUMMARY OF THE INVENTION As a result of extensive investigations, the inventors have found that the above-described objects can be attained by processing a silver halide photographic lightsensitive material containing at least one silver halide emulsion layer and containing a gelatin derivative-containing layer as an uppermost layer in photographic p essing solution maintained at a temperature of at least C.
DETAILED DESCRIPTION OF THE INVENTION The present invention provides the advantage that photographic images having excellent quality photographic and physical properties can rapidly be obtained. That is, the present invention provides the ability to reduce the change in the photographic and physical properties of the light-sensitive material before processing and to conduct rapid photographic processing without a deterioration in the photographic properties, such as fogging, reduction in sensitivity, etc., and with out physical deterioration such as reticulation due to processing at an elevated temperature or over a wide pH range. A further advantage of the present invention is that, since the gelatin derivative incorporated in the uppermost layer provided on a photographic light-sensitive material has excellent solubility, excellent compatibility with other high molecular weight substances, excellent coating properties and the like, no difficulties in the production of photographic light-sensitive materials are encountered.
The gelatin derivative used in the present invention is a chemically modified gelatin which is produced as a result of processing gelatin with a monofunctional agent capable of reacting with an amino group, an imino group, a carboxyl group and/or a hydroxy group, contained in the polar or hydrophilic residue in the various amino acid fractions forming the gelatin molecules. The residue of the functional group containing agent suitably is present in an amount of from about 0.02 to about 1.5m mol/g, preferably from 0.05 to 1.0m mol/g in the gelatin derivative (on a dry basis).
The term gelatin which is used in the present specification as referring to the starting material of the gelatin derivative of the present invention, is also used to described the proteinic substance derived from collagen. Also. this term includes any other products which are substantially equivalent thereto, such as synthetic gelatins. Generally, as gelatin there are known the socalled alkali-processed gelatin" derived from collagen through treatment with lime or the like, the so-called acid-processed gelatin with the processing being with hydrochloric acid or the like, the so-called enzyme-processed gelatin with the processing being with a hydrolase or the like. and low molecular weight gelatin obtained by further hydrolyzing the abovedescribed gelatins using various methods. Any of these gelatins can be used for the production of the gelatin derivative necessary for practicing the present inven tion.
As the monofunctional reagents necessary for preparing the gelatin derivative to be used in the invention, any compound that possesses one functional group per molecule capable of reacting with an amino group, an imino group, a carboxyl group and/or a hydroxy group contained in the gelatin molecule can be used for preparing gelatin derivatives which are substantially equivalent in usefulness in the practice of the present invention. Representative functional groups are illustrated by the following: -NCO, -NCS, --NHCOSO M or NHCS-SO ,M (where M is an alkali metal such as sodium, potassium, etc.
(where R, and R each is a hydrogen atom or a lower alkyl group e.g., having up to 4 carbon atoms such as a methyl group or ethyl group; and X is a halogen atom such as Cl, Br, etc.),
above 0, -CHCH-R 00 o (where R, is as defined above).
(where X is as defined above), -X (where X is as defined above), COOR;,(where R is an aryl group having an electron attracting group at the 0 or p-position (where R is as defined above), and the like.
Representative examples of the agents having a func tional group suitable for preparing the gelatin derivative used in the invention are illustrated below:
isocyanates such as phenyl isocyanate, p-tolyl isocyanate, 4-bromophenyl isocyanate, 4-chlorophenyl isocyanate, 2-nitrophenyl isocyanate, 4-ethoxycarbonylphenyl isocyanate, l-naphthyl isocyanate, phenyl isocyanatebisulfite adduct, p-biphenyl isocyanatebisulfite adduct, etc. or a precursor thereof;
isothiocyanates such as phenyl isothiocyanatc, p'tolyl isothiocyanate, phenyl isothiocyanate-bisulfide adduct, etc. or a precursor thereof;
aziridines such as N-pentanoyl-2-ethyl-l-aziridine, l-phenylcarbamoylaziridine, 2-methyll -phenylcarbamoylaziridine, l-dimethylaminosulfonylaziridinc, lbenzoylazridine, 4nitrobenzyol-l-aziridine, l-(2- chlorophenyl )carbamoyll -aziridine, phenyl)carbamoylaziridine l-( n-butylsulfonyl )aziridine, l-( phenylsulfonyI-Z-methylaziridine, 2-( laziridinyl )-4, 6-bisethylaminol ,3,5-triazine, l-phenyl- 3-(2-chloroethyl)urea, etc. or a precursor thereof;
activated vinyl compounds (eg, Containing groups such as a carbonyl group, a sulfonyl group, etc.) such as N-vinylsulfonyl-p-toluidine. vinylsulfonylbenzene, lmethyl-4-vinylsulfonylbenzene, acrylonitrile, l-(hydroxysulfonyloxy )-2-( 4-methoxyphenylsulfonyl )ethane, Z-phenylcarbamoylethyl bromide, etc. or a precursor thereof;
sulfonyl halides such as, the arylsulfonyl halides, e.g., benzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, 4-phenoxybenzenesulfonyl chloride. 4- chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride. 3- nitrobenzenesulfonyl chloride, 3-carboxybenzenesulfonyl chloride. Z-naphthalenesulfonyl chloride, 4- aminobenzenesulfonyl fluoride, 3,4-diaminobenzenesulfonyl fluoride, 3-carboxybenzenesulfonyl fluoride. etc. and the lower alkylsulfonyl halides such as methanesulfonyl chloride and ethansulfonyl chloride, etc.;
carboxylic acid halides such as the arylcarboxylic acid halides. e.g., 4-nitrobenzoyl chloride, 4-carboxybenzoyl bromide, etc.; and the aliphatic carboxylic acid halides, e.g., butyric acid chloride, caproic acid chloride and caprylic acid chloride. etc,;
carboxylic acid anhydrides including aromatic and aliphatic carboxylic acid anhydrides such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, isatoic acid anhydride, monomethylsuccinic acid anhydride, glutaric acid anhydride. benzoic acid anhydride, trimellitic acid anhydride, 3,6-dichlorophthalic acid anhydride, diglycollic acid anhydride, nitrophthalic acid anhydride, etc.;
oxirane ring-containing compounds such as 3- phenyloxy-l ,2-epoxypropa ne. 3-( 3-methylphenyloxy l,2,-epoxypropane, 3-( 2,4-dibromophenyloxy)-1,2- epoxypropane, 3-(4-acetylaminophenyloxy )-l 2-epoxypropane, 3-( 2-biphenyloxy)-l ,2-epoxypropane, 3- (2,4-dinitrol-naphthoxy l ,2-epoxypropanc, lchloro-2-hydroxy-3-phenyloxypropane, epichlorohyl 3-methyl- (where Y is a lower alkyloxy group; an aryloxy group such as phenox an NH lovtci alkyl group; and
lower alkyl lowcr alkyl or an NH-aryl group such as such as bromoacetic acid, chloroacetic acid, 2- chloro-4,6-dimethoxy-l ,3,5-triazine and 2-chloro-4,6- diethylaminol ,3,S-triazine, etc.;
activated esters of carboxylic acids including aromatic acid and aliphatic acids such as o-nitrophcnyl benzoate, p-nitrophenyl acetate, p-nitrophenyl-lhydroxynaphthoate, etc.; and
maleimides such as N-ethylmaleimide, N-phenylmaleimide, N-(p-carboxyphenyl)-maleimide. N-(p-sulfophenyl )maleimide, N-( carboxymethyl )-maleimide, etc.
These reagents can be used to chemically modify gelatin employing the method to be described hereinafter, and the resulting gelatin derivatives, as the material used in the uppermost layer of the photographic lightsensitive material of the present invention, influence greatly the ability of the photographic light-sensitive of the present invention to the aforesaid aptitude for rapid processing at an elevated temperature. Of the aboveillustrated reagents, isocyanates such as phenyl isocyanate, p-tolyl isocyanate, etc., aziridines such as phenylcarbamoylaziridine, 2-methyll -phenylcarbamoylaziridine, l-dimethylaminosulfonylaziridinc, lbenzoylaziridine, etc., and sulfonyl halides such as benzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride. 4-chlorobenzenesulfonyl chloride, 4-hromobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, etc. are particularly preferred reagents, either because they are economically advantageous due to their availability, or because they have a marked effect in preventing reticulation in processing at higher temperatures, for example, 48C or 52C.
The gelatin derivatives necessary for practicing the present invention can be prepared using a conventional technique by reacting gelatin with the above-described monofunctional reagent (compound having one functional group per molecule capable of reacting with the reactive group in the gelatin molecule) in a solvent for gelatin such as water, an organic solvent (e.g., dimethylsulfoxide, dimethylformamide, acetic acid, etc.) or a mixture of an organic solvent and water, in the presence of, if necessary, a base or an acid as a pH-adjusting agent. The above-described process for preparing the gelatin derivatives used in the present invention is the same as or similar to known processes and described in, e.g., US. Pat. Nos. 2,594,293, 2,614,929, 2,763,639, 3,118,766, 3,132,945, 3,186,846, British Pat. Nos. 648,926, 976,391 and Japanese Patent Publication No. 26845/67.
However, the present invention is clearly distinguished from the above-described known patents. According to the descriptions in the above described patents, all of the objects and the effects thereof relate to processes for the production of gelatin derivatives or to processes for the production of precipitated silver halide emulsions. Therefore, the present invention which relates to the method of incorporating gelatin derivatives prepared by treating gelatin with the foregoing monofunctional reagents, in the uppermost layer of a photographic light-sensitive material for the purpose of producing photographic light-sensitive materials having good characteristics for rapid processing at an elevated temperature, is completely different from the above recited prior art.
In the present invention, the gelatin derivative is not necessarily incorporated in the photographic emulsion layer of a photographic light-sensitive material to be processed at a high temperature. All that is required is that the gelatin derivative be incorporated in the protective layer on an emulsion layer or to provide a layer comprising the gelatin derivative alone as the protective layer on the emulsion layer. in this case, two or more gelatin derivatives can be used in combination. Also, a photographic light-sensitive material used in the invention having good characteristics for rapid processing at an elevated temperature can be obtained by insubstances such as non-modified gelatin, albumin, ca-
sein, agar-agar, sodium alginate, water-soluble starch, etc.; cellulose derivatives such as carboxy cellulose alkyl (e.g., methyl) esters, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.; and synthetic polymers such as polyvinyl alcohol, partially esterified polyvinyl alcohol, polyacrylamide or derivatives thereof, polyvinylpyrrolidone, polyacrylic acid or polyacrylate, or various copolymer thereof, and various copolymers of maleic anhydride and another vinyl compound; etc., are preferable. The ratio of the gelatin derivative to these hydrophilic binders is not particularly limited and can vary; but, in order to markedly promote the effect obtained by the practice of the present invention, the gelatin derivative content is preferably not than based on the weight of total binders forming the uppermost layer.
As the developer employable in the photographic processing in the present invention, any developer capable of reducing silver halide to silver can be used.
1n the case of black-and-white development, developers containing as the developing agent polyhydroxybenzenes, 4-aminophenols, 3-pyrazolidones, pphenylenediamines, ascorbic acid, N-(p-hydroxy phenyl)glycine, other developing agents as disclosed in C.E.K. Mees & TH. James The Theory of Photographic Process, Third Edition 1966) MacMillan Co., Chapter 13 and L.F.A. Mason Photographic Processing Chemistry (Oxford Press 1966) pp 16-30, or a mixture thereof can be used. Suitable polyhydroxy benezenes include, e.g., hydroquinone, Z-methylhydroquinone, 2-phenylhydroquinone, Z-chlorohydroquinone, pyrogallol, catechol, etc. Suitable 4-aminophenol include, e.g., 4-N-methyl-aminophenol hemisulfate (conventionally called Metol"), 4-N-benzyl-aminophenol chloride, 4-N,N-diethylaminophenol chloride, 4- aminophenol sulfate. etc. Suitable 3-pyrazol1dones include, e.g., l-phenyl 3-pyrazolidone, 4,4-dimethyl-lphenyl-3-pyrazolidone, 4-methy1- l -phenyl-3-pyrazolidone, etc.
In the case of color development, developers containing as the developing agent an aromatic primary amines such as p-phenylenediamine, for example, inorganic acid salts of 4-amino-N,N-diethylaniline; 2- amino-5-diethylaminotoluene; 2-amino-5-(N-ethyl-N- laurylamino )toluene; 4-[N-ethyl-N-( fl-hydroxyethyl amino aniline; 3 -methyl-4-amino-N-ethyl-N-( B- hydroxyethyl)aniline; 4-amino-3-methyl-N,N-diethylaniline; 4-amino- 3-methyl-N-ethyl-N-( 2- methanesulfonylaminoethyl)aniline as disclosed in US. Pat. No. 2,193,015; N-( 2-amino-5-diethylaminophenylethyl) methanesulfoamide, N,N-dimethyl-pphenylenediamine as disclosed in US. Pat. No. 2,592,364; 3-methyl-4-amino-N-ethyl-N-methoxyethylaniline as disclosed in Japanese Patent laid open to inspection No. 64933/7 3, or the like can be used. More detailed materials on color developing agents are described in L.F.A. Mason Photographic Processing Chemistry Focal Press-London (1966) pp226-229. 3- pyrazolidones in combination with the color developing agent also can be used.
In order to further promote the effects of the present invention, a hardener, a matting agent, a lubricant or the like can be used in suitable amounts in combination with the gelatin derivative incorporated in the uppermost layer. it is well known, as a means necessary for promoting the effect of the protective layer, to add the above-described gelatin additives to the protective layer of conventional photographic light-sensitive materials. 1n the present invention it is preferable to use them for the same purpose also. That is, a hardener is effective to suitably harden the uppermost layer to maintain the physical strength of the surface layer. Particularly preferred examples of hardeners are: aldehyde series compounds such as formaldehyde, glutaraldehyde and halocarboxyaldehydes (e.g. mucochloric acid); ketones such as diacetyl and cyclopentanedione; active halogen-containing compounds such as bis(2- chloethyl urea), 2-hydroxy-4,6-dichloro-1 ,3,5-triazine and those compounds as disclosed in US. Pat. Nos. 3,288,775 and 2,732,303 and British Pat. Nos. 974,723 and 1,167,207; active olefin-containing compounds such as divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro- 1 ,3,5-triazine and those compounds as disclosed in US. Pat. Nos. 3,635,718; 3,232,763; 3,490,911 and 3,642,486 and British Pat. No. 994,869; N-methylol compounds such as N-hydroxymethylphthalimide and those compounds as disclosed in US. Pat. Nos.
2,732,316 and 2,586,168; isocyanates as disclosed in U.S. Pat. Nos. 3,103,437; aziridines as disclosed in U.S. Pat. Nos. 3,017,280 and 2,983,61 1; acid derivatives as disclosed in U.S. Pat. Nos. 2,725,294 and 2,725,295; carbodiimide series compounds as disclosed in U.S. Pat. Nos. 3,100,704; epoxy compounds as disclosed in U.S. Pat. No. 3,091,537; isooxazol series compounds as disclosed in U.S. Pat. Nos. 3,321,313 and 3,543,292; dioxane derivatives such as dihydroxydioxane and dichlorodioxane and inorganic hardeners such as chrom alum and zirconium sulfate, precursors of the abovedescribed materials such as addition compounds of an alkali metal bisulfite and an aldehyde, methylol derivaties of hydrazine, and primary aliphatic nitro alcohols and those compounds as disclosed in U.S. Pat. Nos. 3,288,775; 3,017,280 and 2,983,611 and British Pat. No. 1,167,207. A matting agent is useful for preventing inconvenient adhesion difficulties between the uppermost layer and the surface of other substances. As the matting agent, there are preferably used silver halide grains of a suitable grain size; inorganic compounds such as silica, strontium barium sulfate, etc.; water-dispersable vinyl polymers such as polymethyl methacrylate, etc. A lubricant is useful for preventing adhesion difficulties similar to the matting agent and, in addition, is effective for improving friction properties which relates to the camera adaptation of movie films upon photographing or projection. Specifically, waxes such as liquid paraffin, higher fatty acid esters, etc.; polyfluorinated hydrocarbons or derivatives thereof; silicones such as polyalkylpolysiloxane, polyarylpolysiloxane, polyalkylpolysiloxane or the alkylene oxide adduct derivaties thereof; and the like are preferably used. These materials are each used for their known purposes and are used suitably in an amount effective to achieve the purpose of their use. An effective amount of the materials can each range from 0.01 to 90% wt., preferably from 0.05 to 50 wt% on a solids basis of the uppermost layer.
If necessary, a coating acid can be used for coating the uppermost layer for the same reasons such is used in coating other hydrophilic colloidal layers constituting a photographic light-sensitive material. Any of the known surface active agents can be employed and specifically, anionic surface active agents containing acidic groups such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfate group, a phosphate group, etc., ampholytic surface active agents of carboxylic acid type, sulfonic acid type, sulfate type or phosphate type; nonionic surface active agents of the polyalkyleneoxide series or the polyglycerin series; and natural surface active agents such as saponin, are preferably used. Suitable such materials and the amounts thereof generally suitable for use are disclosed for example, in U.S. Pat. Nos. 2,600,831,
3,441,413, 3,442,654; 3,475,174; 3,545,974; German OLS No. 1,942,665; and British Pat. Nos. 1077317, and 1 198450.
When the present invention is practiced in this manner, a positive light-sensitive material for movie use, which conventionally has been photographically processed at a temperature as low as 24C for a comparactively long period of time, can be processed at an elevated temperature of, for example, 52C in a short time to thereby form images of high quality.
A temperature preferably not higher than about 60C can be employed. While it is necessary in the method of the present invention to develop the photographic light-sensitive material at a temperature of at least 30C., processings other than development can be practiced at a temperature of some what lower than 30C.
Also, the present invention is markedly effective where it is intended to improve the processing steps of reversal color light-sensitive materials by shortening the processing time. Such steps involve black-andwhite development and color development and, therefore, take a long time in comparison with other lightsensitive materials. That is, the present invention enables reversal color light-sensitive materials to be processed without reticulation resulting when the temperature of the processing steps is changed completely or partially from a low temperature of 24C or 29C to a high temperature of, for example, 38C or 46C and, therefore, enables images to be formed with excellent quality in a short time. In addition, the present invention enables first development, color development, bleach-fixation and like processing to be conducted immediately after photographing, without the necessity for a pre-hardening bath treatment which has conventionally been inevitable with reversal color photo graphic light-sensitive materials. Thus, the present invention provides the advantage that the processing time can be shortened and the processing steps can be reduced in the number of baths required without delaying the developing speed (or reduction in sensitivity) which has been encountered in the case of an exceptional hardening of the photographic layers so as to prevent reticulation.
The detailed mechanism on how reticulation in high temperature-processing can markedly be controlled by providing an uppermost layer comprising or containing the gelatin derivative on a photographic layer coated on a support is not yet completely clear. However, based on assumptions made from the experimental re sults obtained and while not desiring to be bound one factor could be that the swelling behavior, upon photographic processing, of the hydrophilic binder-containing photographic layer provided on a support favorably changes so as to prevent reticulation clue to the influence of the gelatin derivative-containing uppermost layer. That is, it is believed that when a silver halide photographic light-sensitive material with the upper most layer of the gelatin derivative used in the present invention is photographically processed at temperatures of 30C or above, the swelling of the photographic emulsion layer in the direction parallel to the support is restricted as compared with swelling in the vertical direction to the support, thereby contributing to the prevention of reticulation.
It is known that the reticulation, which occurs when a gelatin layer provided in a support is swollen with water, becomes conspicuous when the swelling in the lateral direction along the support becomes great (see Photographic Gelatin, p.60, RJ. Cox, Ed., Academic Press, London (1972)). However, it was found that, when a silver halide photographic light-sensitive material having an uppermost layer containing the gelatin derivative of the present invention is photographically processed at temperatures not at 30C or above, even though swelling in the vertical direction is very great, swelling in the lateral direction is controlled. This was a completely unexpected and surprising discovery.
The gelatin derivative used in the invention can be used as the subbing layer between the support and the photographic emulsion layer, or as the binder for an intermediate layer. a filter layer, a stripping layer or a backing layer. as well as the element for the uppermost layer or for the protective layer.
in practicing the present invention, the photographic layers having the gelatin derivative-containing uppermost layer thereon can include a photographic emulsion layer wherein various silver salts such as silver chloride, silver bromide, silver iodide, and mixed silver halides (e.g., silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc.) are used. Illustrative of such emulsions are various silver halide photographic emulsions such as orthochromatic emulsions, panchromatic emulsions, emulsions for infrared rays, emulsions for recording invisible light such as X-rays, color photographic emulsions (e.g., emulsions containing a color former, emulsions containing a dye developing agent, emulsions containing a bleachable dye, etc.). As the dispersing medium (or binder) for these photographic emulsions, gelatin, colloidal albumin, various gelatin derivatives (e.g., phthaloylated gelatin, malonoylated gelatin, etc.), cellulose derivatives (e.g., cellulose sulfate, hydroxyethyl cellulose, etc.), synthetic high polymers such as polyvinyl compounds (e.g., polyvinyl a1- cohol, polyvinyl pyrrolidone, polyacrylamide, polystyrenesulfonic acid, etc.), gelatin-synthetic high polymer mixtures, and the like can be used. In addition, as the support for the photographic light-sensitive materials used in the present invention, various photographic supports such as a cellulose ester film, a polyvinyl acetate film, a polyethylene terephthalate film, a polystyrene film, relating films, paper, polyethylene-coated paper, synthetic paper, and the like are preferably used.
The silver halide photographic emulsion used in the present invention can be chemically sensitized in a conventional manner. Examples of suitable chemical sensitizers are active gelatin, gold compounds such as chloroanrate and gold chloride as disclosed in US. Pat. Nos. 2,399,083, 2,540,085, 2,597,856 and 2,597,915; salts of noble metals such as platinum, paladium, iridium, rhodium and ruthenium as disclosed in US. Pat. Nos. 2,448,060; 2,540,086; 2,566,245; 2,566,263 and 2,598,079; sulfur compounds which are capable of reacting with silver halide to produce silver sulfide as disclosed in US. Pat. Nos. 1,574,944; 2,410,689; 3,189,458 and 3,501,313; reducing materials such as starmous salts and amines as disclosed in US. Pat. Nos. 2,487,850; 2,518,698; 2,521,928; 2,521,926;
2,694,637; 2,983,610 and 3,201,254.
The silver halide photographic emulsion used can be spectrally sensitized or supersensitized with at least one of the polymethinedyes such as the cyanine dyes including the merocryanine dyes and the like, optionally in combination with a styryl dyestuft" or a substantially colorless aromatic compound. Examples of blue-sensitizing dyes are those as disclosed in US. Pat. Nos. 2,493,748; 2,519,001; 2,977,229; 3,480,434; 3,672,897 and 3,703,377. Examples of green-sensitizing dyes are those as disclosed in US. Pat. Nos. 2,688,545; 2,912,329; 3,397,060; 3,615,635 and 3,628,964; British Pat. Nos. 1,195,302; 1,242,588 and 1,293,862; German OLS Nos. 2,030,326 and 2,121 ,780 and Japanese Patent Publication Nos. 4936/68 and 14030/69. Examples of red-sensitizing dyes are those as disclosed in US. Pat. Nos. 351 1.664;
n coon (JJHZCHZSO 3H) CH CH COOH (Cl-1 0M 50 1-1 N(C 1-1 1 (III) (combination) s H O S v with yellow coupler S (combination) N t 0 f 2 5 CH CH SO H S with yellow coupler I S (combination) 0 N I C 14 (CH SO HN(C H KO S (CH Oi S 0 l (combination) ca cn on (CH SO Na Sensitizing Dyes for the Green-sensitive Layer;
(VII) (combination) (combination) 3 H C O 2 2 C H 3 III 0 S 5 III 3 H 5 2 H 2 N'C 2 H CIIN C n m 5 M H C h n C nw H i I. nw H m k 3 H C 0 C m 3 ,w 3 C 0 N C 5 \J, 3 H 2 5 2 6 H H G 2 C .N NIIC 2 H C'N RIC (XVI) (XVII sensitizing Dyes for the Red-Sensitive Layer:
(XXIII) S on 'CH I 9 N H C H 2 5 (combination) C2 2 N C NH H=CH NH f NH NH (XXIV) S CH=CH-CH-' (CH COOH N I o 2 3 2 5 (combination) N (I) Ol N N SO Na s OOH S CH=C-Cll N N l o (cs 50 (combination) In addition, the photographic emulsion can contain an antifogging agent or a stabilizing agent which is known in the art. Examples of suitable stabilizing agents or antifogging agents are heterocyclic compounds such as 4-hydroxy fi-methyll ,3,3a, 7-tetrazaindene, S-methylbenzothiazole and l-phenyl-S-mercaptotetrazole, mercury-containing compounds, mercapto compounds and metal salts as disclosed in CEK Mees The Theory of The Photographic Process Third Ed.
119661, US. Pat. Nos. 1,758,576; 2,110,178; 213L038; 2,173,628; 2,697,040; 2,304,962; 2324.123; 2,394,198, 2,444,605 -8; 2,566,245; 2,694,716; 2,697,099; 2,708,162; 2,728,633-5, 2,476,536; 2,824,001; 2,843,491, 2,886,437, 3,052,544; 3,137,577; 3,220,839, 3,226,231; 3,236,652; 3,251,691; 3,252,799; 3,287,135;
3,326,681; 3,420,668 and 3,622,339; British Pat. Nos. 893,428: 403,789; 1,736,609 and 1,200,188.
Furthermore, the photographic emulsion and/or the auxiliary layer used in the present invention can contain a hardener, such as an aldehyde, a formaldehyde precursor containing methylol group or alkylarninomethyl group, a 1,4-dioxane, an aziridine, an isoxazole, a carbodiimide, an active halogen containing compound or, an active vinyl compound; a gelatin plasticizer such as an aliphatic alcohol or a glycol; various surface active agents as a coating aid or as an antistatic agent as well known in the art; a ultraviolet absorbant; a fluorescent brightening agent; and antihalation dyes or filter dyes.
The present invention will now be illustrated in greater detail by reference to the following examples of both the process for preparing the gelatin derivative used in the present invention and examples of the present invention. Unless otherwise indicated in the examples given hereinafter, all parts, percents, ratios and the like, are by weight.
PRODUCTION EXAMPLE 1 Phenyl Isocyanate-Processed Gelatin (abbreviated as Gd-l 118 Grams of lime-processed gelatin prepared from cow bone was dissolved in 650 ml of distilled water at 50C and the resulting solution was cooled to 40C. A solution prepared by dissolving 6 g of phenyl isocyanate in 20 ml of acetone was added thereto over a 20 minute period while adding thereto a 10% sodium hydroxide aqueous solution under sufficient stirring in order to mainain the pH of the solution at 9.5. After the addition of the isocyanate solution, stirring was continued for an additional 20 minutes while maintaining the temperature and the pH of the solution at the same levels. Thereafter, the pH of the solution was adjusted to 7 using dilute sulfuric acid (5 wt%) followed by lyophilization. Thus, g of the gelatin derivative (Gd-l as a solid was obtained.
PRODUCTION EXAMPLE 2 l-Pheny1carbamoylaziridine-Processed Gelatin (abbreviated as Gd-2):
700 Grams of the same gelatin as used in Production Example 1 was swollen in 7 liters of distilled water followed by heating to 45C to dissolve. After adjusting the pH of the gelatin aqueous solution to 9.1 using a 6N sodium hydroxide aqueous solution, a solution prepared by dissolving 94.5 g of l-phenylcarbamoylaziridine in ml of dioxane was added thereto over 15 minutes. Then, while maintaining the solution temperature at 45C, the above-described mixed solution was vigorously stirred for 1.5 hours. The pH values decreased to 8.0. After adjusting the pH of the reaction mixture to 6.5 using 6N sulfuric acid, lyophilization was effected to obtain 695 g of the gelatin derivative PRODUCTION EXAMPLE 3 Benzenesulfonyl Chloride-processed Gelatin (abbreviated as Gd-3):
360 Grams of lime-processed inert gelatin prepared from ossein was dispersed in 36 liters of distilled water to swell. Then, after dissolving it by heating to 40C, the pH of the solution was adjusted to 9.5 using a 6N sodium hydroxide aqueous solution. To this solution was added 24.6 g of benzenesulfonyl chloride over a 10 minute period under stirring. Stirring was continued for an additional hour, during which the temperature of the reaction mixture was maintained at 45C and the pH was maintained at 9.5 using a 6N sodium hydroxide aqueous solution. Then, after adjusting the pH of the reaction mixture to 6.5 using 6N sulfuric acid, the mixture was cool-set, cut into pieces and washed for 24 hours with cold water. After redissolving the pieces, the solution was subjected to lyophilization. Thus, 3.8 g of the gelatin derivative (Gd-3) was obtained.
PRODUCTION EXAMPLE 4 4-Methylbenzenesulfonyl Chloride-Processed Gelatin (Gd-4):
500 Grams of the same gelatin as used in Production Example 3 was dissolved in 4 liters of distilled water at 40-50C, and the pH of the solution was adjusted to 9 i 0.l using a 5 wt.% sodium hydroxide aqueous solution. A solution prepared by dissolving 25.5 g of 4- methylbenzenesulfonyl chloride in 100 ml of dioxane was added to the above-described gelatin aqueous solution over a 20 minute period under stirring while maintaining the temperature and the pH at the same levels. After the completion of the addition, the reaction mixture was stirred for 20 minutes at the same pH and the same temperature. Then, the solution was desalted by passing it through a mixed bed of a commercially available cation exchange resin (IR-I20 produced by 01'- gano Co. Ltd.) and a commercially available anion exchange resin (IR-45 produced by Organo Co. Ltd). The pH of the solution, after desalting was adjusted to 6-7 using a dilute caustic aqueous solution. Upon condensing the solution and drying in warm air, 420 g of the gelatin derivative (Gd-4) was obtained.
PRODUCTION EXAMPLE 5 4-Methylbenzenesulfonyl Chloride-Processed Gelatin (Gd-5 The same procedures as described in Production Example 4 were conducted except for changing the amount of 4-methylbenzenesulfonyl chloride from 25.5 g to 34 g and changing the desalting method (the same noodle washing as described in Production Example 3 being conducted instead of ion exchange resin-processing of Production Example 4). Thus, 425 g of the gelatin derivative (Gd-5) was obtained.
PRODUCTION EXAMPLE 6 3-Phenyloxy-l ,2-epoxypropane-Processed Gelatin (Gd-6):
5O Grams of the same gelatin as used in Production Example 4 was dispersed in 500 g of water and dissolved at 55C. To this solution was added a 10% sodium hydroxide aqueous solution to adjust the pH to 9. Then, 25 g of an acetone solution containing l0.8 g of 3-phenyloxyl ,2'epoxypropane was added thereto over a 1 hour period, during which a 10% sodium hydroxide aqueous solution was added incrementally thereto so as to maintain the pH at 9. After the addition of the epoxide, stirring was continued for an additional 2 hours at 55C. After adjusting the pH of the reaction mixture to 7 by adding a 5% sulfuric acid aqueous solution, the reaction mixture was gradually poured into 2 liters of acetone under stirring. The precipitate formed was collected by filtration and air-dried. Thus, 45 g of the gelatin derivative (Gd-6) was obtained.
PRODUCTION EXAMPLE 7 Phthalic Anhydride-Processed Gelatin (Gd-7):
I00 Grams of the same gelatin as used in Production Example 4 was dispersed in l liter of distilled water and dissolved at 40C. To this solution was added a 10% sodium hydroxide aqueous solution under stirring to adjust the pH to 10. 7 Grams of phthalic anhydride, dissolved in g of acetone, was added to the abovedescribed gelatin aqueous solution over about a 15 minute period, during which the temperature and the pH of the reaction mixture were maintained at 40C and 10, respectively. After the completion of the addition, the reaction mixture was stirred for an additional l0 minutes. Then, after adjusting the pH of the solution to 7 with dilute (5 wt.%) sulfuric acid, the reaction mixture was cool-set to gel. After cutting, it was washed and dried. Thus, 82 g of the gelatin derivative (Gd-7) was obtained.
EXAMPLES l 10 The materials used in the following Examples 1 to 10 are given in Tables l to 7.
Table 1 Color Former Name No. I
According to "Waei Yuki-kagaku Mcimciho(Zcn) (Japanese-English Organic Chemical NO- menclaturc lcomplctc]: by Hiruyarna and Hirayama 1972 I) (hereinafter the same).
Table 2 SPltirqi sensitizing A n t o No. l
o C H o 2 s -ci1 i=cH-c e l c ruso O 4 0 l 5 cH c=cH.-c
C1 N N l l C H SO I- c so Table 3 Antihalatiori Layer (hereinafter abbreviated as AH Stabilizing Agent Name, layer): containing black colloidal silver, gelatin,
water and Hardener No. 2;
No. l 4-Hydroxy-6-methyl-l,3,3a.7-tetrazaindene i Na 2 NMehylbenzothiazol-mm Iodide Red-Sensitive Layer (hereinafter abbreviated as N0. 3 l-Phenyl 5-mercaptotetrazolc a gelatino-silver bromoiodide emulsion (containing Table 4 7 mol% of silver iodide) containing Color Former Hardener Name No. 8, Color Former 9, Sensitizing Dye No. 2, Stal Mucochlofic Add bilizing Agent No. l, Hardener No. 2 and Coating No. 2 3-Chloro-2-phenoxymalealdehyd ic Acid Ald N0. 1; 3 gf ziz gif' Gelatin lnterrnediate Layer: containing Coating Aid No. 4 l,3,S-Triacryloylhexahydro-l,3,5-triazine No. l and Coating Aid No. 5, Hardener No. 2 and No. 5 2,3Dihydroxy-S-methyl-l,4-dioxane li d l i No. 6 Fonnaldeh de y l 5 Green-Sensitive Layer (hereinafter abbreviated as Mamng Assn Name Tab 6 GL): a gelatino-silver bromoiodide emulsion layer (containing 7 mol% of silver iodide) containing g lfaghgjggas Grams Color Former No. 3 and Color Former No. 4, Sen- No, 3 Silicon Dioxide Grains sitizing Dye No. l, Stabilizing Agent No. 1, Hard- No. 4 Polymethyl Methacrylate Grains 40 ener N 2 d C i Aid N 1;
Table 6 Coating Aid Name or Structural Formula No l Sodium p-Dodecylbenzenesuifonate No. 2 2-Sulfonato.succinic Acid bis(2-Ethylhexyl)- ester Sodium Salt No. 3 Dimethyltetradecylammonioacetale (internal salt) No. 4 Dimethyldodecylammonioacetate (internal salt) No, 5 C l-l Q -o-(CH,CH,0),.-(cH,),,,-s0,Na n =ol5 Table 7 Yellow Filter Layer (hereinafter abbreviated as YF Ambmcmm Name layer): containing coating Aid No. l, Hardener No. Agent 2, colloidal silver and lime-processed gelatin; and No. 1 Liquid Paraffin Blue-Sensitive Layer (hereinafter abbreviated as No.2 Cetyl Palrnitate BL): a gelatino-silver bromoiodide emulsion layer No. 3 Silicone Oil (containing 7 mol% of silver iodide) containing Color Former No. 2, Stabilizing Agent No. l, and Hardener No. 2. Light-sensitive Material No, 2 (coupler-in-emulsion color reversal film) comprising:
Base: TAC: Subbing Layer: containing gelatin, salicyclic acid, ac-
The kinds and the structures of the emulsion layers used in the examples and additives incorporated in each layer are as follows.
Light-Sensitive Material No. 1 (color negative film) comprising: etone, methanol, methlene chloride and water;
Base: triacetyl cellulose (hereinafter abbreviated as AH Layer: containing black colloidal silver, gelatin,
TAC); water and Hardener No. 2',
Subbing Layer: containing gelatin, salicylic acid, acetone, methanol, methylene chloride and water;
RL: a gelatino-silver bromoiodide emulsion layer (containing 0.5 mol% of silver iodide) containing Color Former No. 9, Spectral Sensitizing Agent No. 2, Stabilizing Agent No. I, Hardener No. 3 and Coating Aid No. l;
Gelatin Intermediate Layer: containing Hardener No. 3 and Coating Aid No. 1;
GL: a gelatino-silver bromoiodide emulsion layer (containing 0.8 mol% of silver iodide) containing Color Former No. 4, Spectral Sensitizing Agent No. l, Stabilizing Agent No. I, Hardener No. 3, and Coating Aid No. l;
YF Layer: containing Hardener No. 3, Coating Aid No. l and colloidal silver; and
BL: a gelatino-silver bromoiodide emulsion layer (containing l mol% of silver iodide) containing Color Former No. l, Stabilizer No. l, Hardener No, 3, and Coating Aid No. 1.
Light-Sensitive Material No. 3 (color positive film) comprising:
Subbing Layer: containing gelatin, salicylic acid, acetone, methanol, methylene chloride and water;
BL: a gelatino-silver bromoiodide emulsion layer (containing 1.2 mol% of silver iodide) containing Color Former No. l, Stabilizer No. l and Stabilizer No. 2, Hardener No. 3, Coating Aid No. I and Coating Aid No. 5;
Gelatin Intermediate Layer: containing Hardener No. 3, Coating Aid No. 1 and Coating Aid No. 5;
RL: a gelatino-silver chlorobromide emulsion layer (containing 45 mol% of silver bromide) containing Color Former No. 6, Spectral Sensitizing Agent No. 2, Stabilizer No. l, Stabilizer No. 2, Hardener No. 3, Coating Aid No. l and Coating Aid No. S;
Gelatin Intermediate Layer: containing Hardener No. 3, Coating Aid No. l and Coating Aid No. 5; and
GL: a gelatino-silver chlorobromide emulsion layer (containing 45 mol% of silver bromide) containing Color Former No. 4, Spectral Sensitizing Agent No. l, Stabilizing Agent No. l, Stabilizing Agent No. 2, Hardener No. 3, Coating Aid No. l and Coating Aid No. 5.
Light-Sensitive Material No. 4 (color paper) comprising:
Base: polyethylene-coated paper;
Subbing Layer: containing gelatin, ethanol and water;
BL: a gelatino-silver chlorobromoiodide emulsion layer (containing l mol% of silver iodide) containing Color Former No. l, Stabilizer No. 1, Hardener No. 3, Hardener No. 4 and Coating Aid No. l;
Gelatin Intermediate Layer: containing Hardener No. 3, Hardener No. 4, and Coating Aid No. 1;
RL: a gelatino-silver chlorobromide emulsion layer (containing 50 mol% of silver bromide) containing Color Former No. 7 Spectral sensitizing Agent No.
2, Stabilizing Agent No. 1, Hardener No. 3, Hardener No. 4 and Coating Aid No. l.
Light-Sensitive Material No.5(coupler-free reversal color film) comprising:
Base: polyethylene te rephthalate;
Subbing Layer: containing gelatin, salicyclic acid, ni-
trocellulose, methylene chloride, acetone, phenol and water,
RL: a gelatino-silver bromoiodide emulsion layer (containing l mol% of silver iodide) containing Spectral Sensitizing Agent No. 2, Stabilizing Agent No. l Stabilizing Agent N0. 3, Hardener No. 6 and Coating Aid No. 1;
GL: a gelatino-silver bromoiodide emulsion layer (containing 4 mol% of silver iodide) containing Spectral Sensitizing Agent No. l, Stabilizing Agent No. l Stabilizing Agent No. 3, Hardener No. 6 and Coating Aid No. l;
YF Layer: containing Hardener No. 6, Coating Aid No. l and colloidal silver; and
BL: a gelatino-silver bromoiodide emulsion layer (containing 4 mol% of silver iodide) containing Stabilizing Agent No. l, Stabilizing Agent No. 3,
Hardener No. 6 and Coating Aid No. l. The processing temperatures, processing periods of time and compositions of the processing solutions used in the samples are given below.
Processing No. l
Color Development 1 '30" Rinsing l5" Bleach-Fixation l '30" Washing with Water I '30" 52C Stabilizing l0" Rinsing 5" As the compositions of the processing solutions, those for color positive materials of those described in Journal of the Society of Motion Picture and Television Engineers, 61, pp.667-701 (I953) were employed per se, as follows:
Processing No. 2:
Color Development (containing p-phenylenediarnine color developing agent and bromide) Bleach-Fixing (containing EDTA-iron salt and thiosulfate) Washing with Water Stabilizing Bath (containing a buffer agent) Processing No, 3:
Color Development Stop-Fixing Washing with Water Bleaching Washing with Water Hardening and Fixing Washing with Water Stabilizing Rinsing 27C 30C 27C 30C 27C 30C 27C The compositions of the processing solutions were the same as described in The British Journal of Photography, I968, Oct. 27th number, pp.83 8-840 as follows: The compounds were dissolved in the order indicated, at a maximum temperature of 35C.